Organic compounds and electronic device comprising organic layer comprising organic compounds

ABSTRACT

Organic compounds suitable for organic layers of electronic devices that show reduced driving voltage, increased luminous efficiency and/or increased power efficiency.

FIELD OF THE INVENTION

The present invention relates to organic compounds, and an electronic device comprising an organic layer comprising the organic compounds.

INTRODUCTION

Organic light emitting diodes (OLEDs) are used in display devices that employ stacks of films containing organic aromatic compounds as electron transport layers (ETLs) and hole transport layers (HTLs). To compete with other displays such as liquid crystal displays (LCDs), it is important to develop materials with properties including reduced driving voltage, increased luminous efficiency and/or increased power efficiency to minimize power consumption in OLED displays, especially for mobile applications where batteries are used as power sources. There have been a tremendous amount of research to develop materials to reduce driving voltages and increase luminous efficiency, mostly for hole injection materials (HIMs), such as described in Synthetic Metals, 2009, 159, 69 and J. Phys. D: Appl. Phys. 2007, 40, 5553. For hole transport layers, materials such as N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl]-4,4′-diamine (NPB) have traditionally been used to provide luminescent properties. There remains a need for new compounds suitable for preparing hole transport layers of OLEDs which have improved properties than those comprising traditional, e.g., NPB-based, hole transport layers.

SUMMARY OF THE INVENTION

The present invention provides novel organic compounds, and an electronic device comprising an organic layer comprising the organic compounds. The electronic device of the present invention shows lower driving voltage, higher luminous efficiency and higher power efficiency than devices comprising NPB as a hole transport material.

In a first aspect, the present invention provides organic compounds having the structure represented by Formula (1):

wherein R₁, R₃, and R₄ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl;

R₂ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ with R₂, R₂ with R₃, or R₃ with R₄ may optionally form one or more ring structures;

R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl;

R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a halogen, a cyano, a hydroxyl, a carbonyl, and a substituted amino group having the structure of

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; with the proviso that at least one of R₆ and R₇ is the substituted amino group; and

L₁ and L₂ are each independently selected from the following structure:

wherein A₁ is selected from a substituted or unsubstituted heteroatom selected from O, P, S, NR′, PR′, or P(═O)R′; wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl;

A₂ through A₅ are each independently selected from CR′₂ or a substituted or unsubstituted heteroatom selected from N, P, PR′₂, or P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl;

A₆ through A₁₁ are each independently selected from CH, N, P, PR′₂, P(═O), or C; and provided that A₆ through A₁₁ each independently represent C only when they are bonded to the indole moiety or X; and

X is a chemical bond or selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; and X may form one or more rings with the ring it is bonded to.

In a second aspect, the present invention is an electronic device comprising an organic layer, wherein the organic layer comprises the organic compounds of the first aspect.

DETAILED DESCRIPTION OF THE INVENTION

The organic compounds of the present invention may have the structure represented by Formula (1):

In Formula (1), L₁ and L₂ may be the same or different. L₁ and L₂ may each independently have the structure represented by Formula (L′),

wherein A₁ may be a substituted or unsubstituted heteroatom selected from O, P, S, NR′, PR′, or P(═O)R′; wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl. Two or less of A₂ through A₅ may be the substituted or unsubstituted heteroatom. Preferred substituted or unsubstituted heteroatoms are N, P, PR′₂, or P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl. L₁ and L₂ may be each independently selected from the following structure:

wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl.

In some embodiments, L₁ and L₂ each independently have the structure represented by Formula (L″),

Preferably, three or less of A₆ through A₁₁ are each independently selected from N, P, PR′₂, or P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl; and provided that A₆ through A₁₁ are each C only when they are bonded to the indole moiety or X. L₁ and L₂ may be each an substituted or unsubstituted arylene, for example, a substituted or unsubstituted C₆-C₆₀ arylene, C₆-C₃₀ arylene, C₆-C₂₀ arylene, or C₆-C₁₂ arylene.

In some embodiments, X is a chemical bond. “Chemical bond” herein means that two groups bonded to the chemical bond are directly linked to each other. For example, when X is a chemical bond, it means that R₆ or R₇ is directly linked to the ring formed by A₁ through A₅, or the ring formed by A₆ through A₁₁.

Examples of L₁ and L₂ include

The organic compound of the present invention may have the structure represented by Formula (2),

wherein X₁ and X₂ may be the same or different. X₁ and X₂ may be each a chemical bond, or each independently selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; and R₁ through R₇ are as previously defined with reference to Formula (1).

When only one of R₆ and R₇ is the substituted amino group, Formula (2) may be represented by Formula (2a) or Formula (2b),

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl and preferably a substituted or unsubstituted C₆-C₆₀ aryl; R₆ in Formula (2b) and R₇ in Formula (2a) are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₆-C₅₀ aryloxy, a substituted or unsubstituted C₁-C₆₀ arylthio, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ through R₅, and X₁ and X₂ are as previously defined with reference to Formula (2). In one embodiment, R₆ in Formula (2b) and R₇ in Formula (2a) are each independently F. More preferably, R₆ in Formula (2b) is F, and X₁ is a chemical bond. More preferably, R₇ in Formula (2a) is F and X₂ is a chemical bond.

In some preferred embodiments, the organic compounds of the present invention have the structure represented by Formula (2c) or (2d):

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl, and preferably a substituted or unsubstituted C₆-C₆₀ aryl; and R₁ through R₅, and X₁ and X₂ are as previously defined with reference to Formula (2).

The organic compounds of the present invention may have the structure represented by Formula (3):

wherein A₇ and A₇′ are each C;

A₆ and A₆′, A₈ through A₁₁, and A₈′ through A₁₁′ are each independently selected from CH, N, P, PR′₂, and P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl; and provided that A₆ and A₈ through A₁₁ are each independently C only when they are bonded to the indole moiety or X₁, and A₆′ and A₈′ through A₁₁′ are each independently C only when they are bonded to the indole moiety or X₂. Preferably, three or less of A₆ and A₈ through A₁₁, and three or less of A₆′ and A₈′ through A₁₁′ are N; and

X₁ and X₂ are each a chemical bond, or each independently selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; X₁ and X₂ may each independently form one or more rings with the rings they are bonded to; and

R₅ through R₇ are as previously defined with reference to Formula (1).

The organic compounds of the present invention may have the structure represented by Formula (3-I):

wherein R₁ through R₇ are as previously defined with reference to Formula (1), and A₆ through A₁₁, A₆′ through A₁₁′, and X₁ and X₂ are as previously defined with reference to Formula (3); with the proviso that at least one of R₁ through R₄, R₆ and R₇ is F or a fluoro-containing C₁-C₃₀ alkyl or C₆-C₆₀ aryl group, preferably a fluoro-containing C₁-C₂₀ alkyl or C₁₋₁₀ alkyl group, or a fluoro-containing C₆-C₃₀ aryl or C₆-C₂₀ aryl group. In one embodiment, at least one of R₁ through R₄ is F, the remaining R₁ through R₄ are each hydrogen, and R₅ is —CH₃. In another embodiment, one of R₆ and R₇ is F, the other one of R₆ and R₇ is the substituted amino group, and R₅ is —CH₃. Surprisingly, the organic compound having the structure of Formula (3-I) (with F or a fluoro-containing substituent) can provide a device comprising a layer of such organic compound with further improved efficiency.

X in Formula (1); X₁ and X₂ in Formulae (2), (2a), (2b), (3) and (3-I); X₁ in Formula (2c); and X₂ in Formula (2d) are each independently a chemical bond, or each independently selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, C₁-C₃₀ alkylene, C₁-C₂₀ alkylene, or C₁-C₁₀ alkylene; a substituted or unsubstituted C₃-C₅₀ cycloalkylene, C₃-C₃₀ cycloalkylene, C₄-C₂₀ cycloalkylene, or C₅-C₁₀ cycloalkylene; a substituted or unsubstituted C₆-C₆₀ arylene, C₆-C₃₀ arylene, C₆-C₂₀ arylene, or C₆-C₁₂ arylene; and a substituted or unsubstituted C₁-C₆₀ heteroarylene, C₁-C₃₀ heteroarylene, C₁-C₂₀ heteroarylene, or C₁-C₁₀ heteroarylene. In some embodiments, X, X₁, and X₂ are each a chemical bond. Examples of X, X₁, and X₂ include

In Formulae (1), (2), (2a), (2b), (2c), (2d), (3) and (3-I), R₅ can be a substituted or unsubstituted C₁-C₃₀ alkyl, C₁-C₂₀ alkyl, C₁-C₁₀ alkyl, C₁-C₅ alkyl, or C₁-C₃ alkyl; a substituted or unsubstituted C₃-C₅₀ cycloalkyl, C₄-C₃₀ cycloalkyl, C₄-C₂₀ cycloalkyl, or C₄-C₁₂ cycloalkyl; a substituted or unsubstituted C₆-C₆₀ aryl, C₆-C₃₀ aryl, C₆-C₂₀ aryl, or C₆-C₁₂ aryl; or a substituted or unsubstituted C₁-C₆₀ heteroaryl, C₁-C₃₀ heteroaryl, C₂-C₂₀ heteroaryl, or C₄-C₁₂ heteroaryl. Preferably, R₅ is selected from —CH₃, —CH₂CH₃,

More preferably, R₅ is —CH₃.

In Formulae (1), (2), (3), and (3-I), respectively, R₆ and R₇ may be the same or different. One or both of R₆ and R₇ is an amino group substituted with a substituted or unsubstituted C₆-C₆₀ aryl or a substituted or unsubstituted C₁-C₆₀ heteroaryl (hereinafter “substituted amino group”).

The substituted amino group in the organic compounds of the present invention may be represented by Formula (A),

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl. In some embodiments, only one of R₆ and R₇ is the substituted amino group. In Formula (1), (2), (3), and (3-I), preferably one of R₆ and R₇ is the substituted amino group, and the other one of R₆ and R₇ is selected from hydrogen, a halogen such as F, or a substituted or unsubstituted C₆-C₆₀ aryl.

The substituted amino group in Formulae (1), (2), (2a), (2b), (2c), (2d), (3) and (3-I); and the substituted amino group of Formula (A) may be each independently selected from the following structures represented by Formula (4a) through Formula (4c):

wherein Ar₃ and Ar₄ are each independently a unsubstituted C₆-C₆₀ aryl, Ar₅ through Ar₇ are each independently a unsubstituted C₆-C₄₀ aryl, and Ar₈ through Ar₁₁ are each independently a unsubstituted C₆-C₃₀ aryl; and X₃ through X₅ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ arylene and a substituted or unsubstituted C₁-C₆₀ heteroarylene. Preferably, at least one of R₆ and R₇ has the structure of Formula (4a). X₃ through X₅ may be each independently selected from a substituted or unsubstituted C₆-C₆₀ arylene, C₆-C₃₀ arylene, C₆-C₂₀ arylene, or C₆-C₁₂ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene, C₁-C₃₀ heteroarylene, C₂-C₂₀ heteroarylene, or C₄-C₁₂ heteroarylene. Preferably, Ar₃ through Ar₁₁ may be each a unsubstituted C₆-C₃₀ aryl, C₆-C₂₀ aryl, C₆-C₁₅ aryl, or C₆-C₁₂ aryl.

Examples of suitable substituted amino groups in the organic compounds of the present invention include the following structures (5-1) through (5-6):

In Formulae (1), (2), (A), (2a), (2b), (2c), (2d), (3) and (3-I), respectively, Ar₁ and Ar₂ are each independently selected from a substituted or unsubstituted C₆-C₆₀ aryl, C₆-C₃₀ aryl, C₆-C₂₀ aryl, or C₆-C₁₅ aryl; or a substituted or unsubstituted C₁-C₆₀ heteroaryl, C₁-C₃₀ heteroaryl, C₂-C₂₀ heteroaryl, or C₄-C₁₂ heteroaryl. Preferably, Ar₁ and Ar₂ are each a substituted or unsubstituted C₆-C₆₀ aryl, C₆-C₃₀ aryl, C₆-C₂₀ aryl, or C₆-C₁₅ aryl. More preferably, Ar₁ and Ar₂ are each independently a substituted or unsubstituted C₁₂-C₃₀ aryl.

In Formulae (1) and (2), (2a), (2b), (2c), (2d) and (3-I), respectively, R₁ through R₄ can be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C₁-C₅₀ alkyl, C₁-C₃₀ alkyl, C₁-C₂₀ alkyl, or C₁-C₁₀ alkyl; a substituted or unsubstituted C₁-C₆₀ heteroaryl, C₁-C₃₀ heteroaryl, C₂-C₂₀ heteroaryl, or C₄-C₁₂ heteroaryl; an alkoxy or an alkoxycarbonyl containing a C₁-C₅₀ alkyl, C₁-C₃₀ alkyl, C₁-C₂₀ alkyl, or C₁-C₁₀ alkyl; a substituted or unsubstituted C₆-C₅₀ aryloxy, C₆-C₃₀ aryloxy, C₆-C₂₀ aryloxy, or C₆-C₁₀ aryloxy; a substituted or unsubstituted C₆-C₅₀ arylthio, C₆-C₃₀ arylthio, C₆-C₂₀arylthio, or C₆-C₁₀ arylthio; a halogen such as F, Cl, Br or I; a cyano; a hydroxyl; and a carbonyl. R₁ and R₂, R₂ and R₃, or R₃ and R₄ may form a 4- to 8-membered fused ring, respectively. R₁, R₃ and R₄ can also be each independently selected from hydrogen, a halogen, a substituted or unsubstituted C₆-C₆₀ aryl, C₆-C₃₀ aryl, C₆-C₂₀ aryl, or C₆-C₁₂ aryl. Preferably, R₁, R₃ and R₄ are each independently selected from hydrogen, F, methyl, phenyl, naphthyl, or biphenyl. In some embodiments, at least two of R₁ through R₄ are hydrogen, and preferably R₂ and R₄ are hydrogen. More preferably, all R₁ through R₄ are hydrogen. In some other embodiments, at least one of R₁ through R₄ is F. More preferably, at least one of R₁ through R₄ is F and the remaining R₁ through R₄ are each hydrogen.

The organic compounds of the present invention may be selected from the following compounds (1) through (36):

The organic compounds of the present invention may have a molecular weight of 500 g/mole or more, 600 g/mole or more, or even 700 g/mole or more, and at the same time, 1,000 g/mole or less, 900 g/mole or less, or even 800 g/mole or less.

The organic compounds of the present invention may have a glass transition temperature (T_(g)) of 110° C. or higher, 130° C. or higher, or 150° C. or higher, and at the same time, 250° C. or lower, 220° C. or lower, or even 200° C. or lower, as measured according to the test method described in the Examples section below.

The organic compounds of the present invention may have a decomposition temperature (T_(d)) at 5% weight loss of 300° C. or higher, 350° C. or higher, or 400° C. or higher, and at the same time, 650° C. or lower, 600° C. or lower, or even 550° C. or lower, as measured according to the test method described in the Examples section below.

The organic compounds of the present invention may be prepared as shown in, for example, Scheme 1 below. An arylhydrazine hydrochloride may react with a ketone derivative of Structure 1 through a Fischer indole synthesis reaction to give an indole derivative of Structure 2. Conditions and raw materials used in Fischer indole synthesis reaction may be those as described in J. Org. Chem., 2012, 77, 8049. Examples of suitable catalysts for the Fischer indole synthesis include brønsted acids such as HCl, H₂SO₄, polyphosphoric acid, and p-toluenesulfonic acid; and Lewis acids such as boron trifluoride, zinc chloride, iron chloride, and aluminium chloride; or mixtures thereof. Then the indole derivative may react with a halogen containing compound with the structure of R₅X¹, wherein L₁, L₂ and R₁ through R₅ are as previously defined with reference to Formula (1) and X¹ is a halogen such as F, Cl, Br or I, and preferably Br or I. The resultant compound of Structure 3 may undergo a Buchwald-Hartwig coupling reaction with an amine compound substituted with a substituted or unsubstituted C₆-C₆₀ aryl or a substituted or unsubstituted C₁-C₆₀ heteroaryl.

The organic compounds of the present invention may be used as charge transport layers and other organic layers in electronic devices, such as OLED devices. For example, the organic compounds of the present invention may be used as charge blocking layers and charge generation layers.

The invention also provides a film comprising at least one layer comprising the organic compounds of the present invention described above.

The present invention also provides an electronic device comprising an organic layer comprising the organic compounds of the present invention. The term “electronic device” herein refers to a device which depends on the principles of electronics and uses the manipulation of electron flow for its operation. The electronic device may include organic photovoltaic, organic field effect transistor, and a light emitting device such as OLED devices. The term “light emitting device” herein refers to a device that emits light when an electrical current is applied across two electrodes.

The organic device of the present invention may comprise a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic compounds of the present invention. The organic layer can be a charge transfer layer that can transport charge carrying moieties, either holes or electrons. The organic layer may comprise a hole transport layer, an emissive layer, an electron transport layer, or a hole injection layer. Preferably, the organic layer is a hole transport layer or a hole injection layer. In addition to the organic compounds of the present invention, the organic layer may comprise one or more dopants. “Dopant” refers to an electron acceptor or a donator that increases the conductivity of an organic layer of an organic electronic device, when added to the organic layer as an additive. Organic electronic devices may likewise be influenced, with regard to their electrical conductivity, by doping. The organic layer comprising the organic compounds of the present invention may be prepared by evaporative vacuum deposition or solution process such as spin coating and ink-jet printing.

In the present invention, “aryl” refers to an organic radical derived from aromatic hydrocarbon by the removal of one hydrogen atom therefrom. An aryl group may be a monocyclic and/or fused ring system each ring of which suitably contains from 4 to 6, preferably from 5 or 6 atoms. Structures wherein two or more aryl groups are combined through single bond(s) are also included. Examples of aryls include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, benzofluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphtacenyl, fluoranthenyl and the like. The naphthyl may be 1-naphthyl or 2-naphthyl. The anthryl may be 1-anthryl, 2-anthryl or 9-anthryl. The fluorenyl may be any one of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.

In the present invention, “substituted aryl” refers to an aryl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom. Heteroatoms may include, for example, O, N, P and S. The chemical group containing at least one heteroatom herein may include, for example, OR′, NR′₂, PR′₂, P(═O)R′₂, SiR′₃; where each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl.

In the present invention, “heteroaryl” refers to an aryl group, in which at least one carbon atom or CH group or CH₂ group is substituted with a heteroatom (for example, B, N, O, S, P(═O), Si and P) or a chemical group containing at least one heteroatom. The heteroaryl may be a 5- or 6-membered monocyclic heteroaryl or a polycyclic heteroaryl which is fused with one or more benzene ring(s), and may be partially saturated. The structures having one or more heteroaryl group(s) bonded through a single bond are also included. The heteroaryl groups may include divalent aryl groups of which the heteroatoms are oxidized or quarternized to form N-oxides, quaternary salts, or the like. Specific examples include, for example, monocyclic heteroaryl groups, such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl; polycyclic heteroaryl groups, such as benzofuranyl, fluoreno[4, 3-b]benzofuranyl, benzothiophenyl, fluoreno[4, 3-b]benzothiophenyl, isobenzofuranyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothia-diazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl and benzodioxolyl; and corresponding N-oxides (for example, pyridyl N-oxide, quinolyl N-oxide) and quaternary salts thereof.

In the present invention, “substituted heteroaryl” refers to a heteroaryl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom. Heteroatoms may include, for example, O, N, P and S. The chemical group containing at least one heteroatom may include, for example, OR′, NR′₂, PR′₂, P(═O)R′₂, or SiR′₃, wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl.

In the present invention, “hydrocarbyl” refers to a chemical group containing only hydrogen and carbon atoms.

In the present invention, “alkyl” and other substituents containing “alkyl” moiety include both linear and branched species. Examples of alkyls include methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, pentyl, or hexyl.

In the present invention, “substituted alkyl” refers to an alkyl in which at least one hydrogen atom is substituted with a heteroatom or a chemical group containing at least one heteroatom. Heteroatoms may include, for example, O, N, P and S. The chemical group containing at least one heteroatom herein may include, for example, OR′, NR′₂, PR′₂, P(═O)R′₂, or SiR′₃; where each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl.

In the present invention, “cycloalkyl” includes a monocyclic hydrocarbon and a polycyclic hydrocarbon such as substituted or unsubstituted adamantyl or substituted or unsubstituted C₇-C₃₀ bicycloalkyl.

In the present invention, other substituted groups described herein have one or more substituents. Substituents may include, for example, deuterium, halogen, C₁-C₃₀ alkyl with or without halogen substituent(s), C₆-C₃₀ aryl, C₁-C₃₀ heteroaryl with or without C₆-C₃₀ aryl substituent(s), a 5- to 7-membered heterocycloalkyl containing one or more heteroatom(s) selected from, for example, B, N, O, S, P(═O), Si and P, a 5 to 7-membered heterocycloalkyl fused with one or more aromatic ring(s), C₃-C₃₀ cycloalkyl, C₅-C₃₀ cycloalkyl fused with one or more aromatic ring(s), tri(C₁-C₃₀) alkylsilyl, di(C₁-C₃₀)alkyl(C₆-C₃₀)arylsilyl, tri(C₆-C₃₀)arylsilyl, adamantyl, C₇-C₃₀ bicycloalkyl, C₂-C₃₀ alkenyl, C₂-C₃₀ alkynyl, cyano, carbazolyl; BR₈R₉, PR₁₀R₁₁, P(═O)R₁₂R₁₃ wherein R₈ through R₁₃ independently represent C₁-C₃₀ alkyl, C₆-C₃₀ aryl or C₁-C₃₀ heteroaryl; C₁-C₃₀ alkyloxy, C₁-C₃₀ alkylthio, C₆-C₃₀ aryloxy, C₆-C₃₀ arylthio, C₁-C₃₀ alkoxycarbonyl, C₁-C₃₀ alkylcarbonyl, C₆-C₃₀ arylcarbonyl, C₆-C₃₀ aryloxycarbonyl, C₁-C₃₀ alkoxycarbonyloxy, C₁-C₃₀ alkylcarbonyloxy, C₆-C₃₀ arylcarbonyloxy, C₆-C₃₀ aryloxycarbonyloxy, carboxyl, nitro and hydroxyl; or that the substituents are linked together to form a ring. For example, a substituent may form a ring structure with one or more atoms on the backbone molecule comprising said substituent.

EXAMPLES

The following examples illustrate embodiments of the present invention. All parts and percentages are by weight unless otherwise indicated.

All solvents and reagents were obtained from commercial vendors, and were used in the highest available purities, and/or when necessary, recrystallized before use. Dry solvents were obtained from an in-house purification/dispensing system (hexane, toluene, and tetrahydrofuran), or purchased from Sigma-Aldrich. All experiments involving “water sensitive compounds” were conducted in “oven dried” glassware, under nitrogen (N₂) atmosphere, or in a glovebox. Reactions were monitored by analytical thin-layer chromatography (TLC) on precoated aluminum plates (VWR 60 F254), visualized by UV light and/or potassium permanganate staining. Flash chromatography was performed on an ISCO COMBIFLASH system with GRACERESOLV cartridges.

Material name Chemical structure/Abbreviation Supplier CAS No. 4-bromophenylacetic acid

Energy Chemical 1878-68-8 Phenylhydrazine hydrochloride

Sinopharm Chemical Reagent Co., Ltd. 59-88-1 Iodobenzene

591-50-4 N,N′-dimethylethylenediamine

110-70-3 N-([1,1′-biphenyl]-4-yl)-9,9- dimethyl-9H-fluoren-2-amine

897671-69-1 2-(dicyclohexylphosphino)- X-Phos 564483-18-7 2′,4′,6′-triisopropylbiphenyl Palladium acetate Pd(OAc)₂ 3375-31-3 Iodomethane CH₃I 74-88-4 Sodium hydride oil dispersion NaH 7646-69-7

The following standard analytical equipment and methods are used in the Examples.

Modeling

All computations utilized the Gaussian09 program as described in Gaussian 09, Revision A.02, Frisch, M. J. et al., Gaussian, Inc., Wallingford Conn., 2009. The calculations were performed with the hybrid density functional theory (DFT) method, B3LYP as described in Becke, A. D. J. Chem. Phys. 1993, 98, 5648; Lee, C. et al., Phys. Rev B 1988, 37, 785; and Miehlich, B. et al. Chem. Phys. Lett. 1989, 157, 200; and the 6-31G* (5d) basis set as described in Ditchfield, R. et al., J. Chem. Phys. 1971, 54, 724; Hehre, W. J. et al., J. Chem. Phys. 1972, 56, 2257; and Gordon, M. S. Chem. Phys. Lett. 1980, 76, 163. The singlet state calculations use the closed shell approximation, and the triplet state calculations use the open shell approximation. All values are quoted in electronvolts (eV). The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) values are determined from the orbital energies of the optimized geometry of the singlet ground state. The triplet energies are determined as the difference between the total energy of the optimized triplet state and the optimized singlet state. A procedure, as described in Lin, B. C et al., J. Phys. Chem. A 2003, 107, 5241-5251, is applied to calculate the reorganization energy of each molecule, with which as the indicator of electron and hole mobility.

NMR

¹H-NMR spectra (500 MHZ or 400 MHZ) are obtained on a Varian VNMRS-500 or VNMRS-400 spectrometer at 30° C. The chemical shifts are referenced to tetramethyl silane (TMS) (6:000) in CDCl₃.

Differential Scanning Calorimetry (DSC)

DSC measurements are carried out on a TA Instruments Q2000 instrument at a scan rate of 10° C./min under N₂ atmosphere for all cycles. The sample (about 7-10 mg) is scanned from room temperature to 300° C., cooled to −60° C., and reheated to 300° C. T_(g) is measured on the second heating scan. Data analysis is performed using TA Universal Analysis software. The T_(g) value is calculated using an “onset-at-inflection” methodology.

Thermal Gravimetric Analysis (TGA)

TGA measurements are carried out on a TA Instruments TGA-Q500 under N₂ atmosphere. The sample (about 7-10 mg) is weighed in a platinum standard plate and loaded into the instrument. The sample is first heated to 60° C. and equilibrated for 30 minutes to remove solvent residues in the sample. Then the sample is cooled to 30° C. The temperature is ramped from 30° C. to 600° C. with 10° C./min rate and the weight change is recorded to determine the decomposition temperature (T_(d)) of the sample. The temperature-weight % (T-Wt %) curve is obtained by TGA scan. The temperature at the 5% weight loss is determined as T_(d).

Liquid Chromatography-Mass Spectrometry (LC/MS)

A sample is dissolved in tetrahydrofuran (THF) at around 0.6 mg/mL. 5 μL sample solution is injected on an Agilent 1220 HPLC/G6224A TOF mass spectrometer. The following analysis conditions are used:

Column: 4.6×150 mm, 3.5 μm ZORBAX Eclipse Plus C₁₈; column temperature: 40° C.; Mobile phase: THF/deioned (DI) water=65/35 volume ratio (Isocratic method); Flow rate: 1.0 mL/min; and

MS conditions: Capillary Voltage: 3500 kV (Pos); Mode: Pos; Scan: 100-2000 amu; Rate: is/scan; and Desolvation temperature: 300° C.

High Performance Liquid Chromatography (HPLC)

A sample is dissolved in THF at around 0.6 mg/mL. The sample solution is at last filtrated through a 0.45 μm syringe filter and 5 μL of the filtrate is injected to HPLC system. The following analysis conditions are used:

Injection volume: 5 μL; Instrument: Agilent 1200 HPLC; Column: 4.6×150 mm, 3.5 μm ZORBAX Eclipse Plus C18; Column temperature: 40° C.; Detector: DAD=250, 280, 350 nm; Mobile Phase: THF/DI water=65/35 volume ratio (Isocratic method); and Flow rate: 1 mL/min.

Synthesis of Compound 1

To a solution of (4-bromophenyl)acetic acid (20 mmol) in dichloromethane (30 mL) were added thionyl chloride (30 mmol) and two drops of N,N-dimethylformamide (DMF) (0.1 mL), and the resulting solution was stirred at room temperature (20-25° C.) for 5 hours under N₂ atmosphere. After that, excessive thionyl chloride was evaporated under vacuum and the residue was stirred with benzene (60 mmol) at 0° C. under N₂ atmosphere. Aluminum (III) chloride (22 mmol) was added slowly in three portions and then stirred at room temperature for 4 hours. The reaction mixture was then poured onto chopped ice in a flask, extracted with dichloromethane (40 mL×3), and washed with brine. The resulting organic phase was dried under reduced pressure and washed with hexane to give Compound 1 with a yield of 90%.

Synthesis of Compound 2

In a 100 mL three-necked flask equipped with a reflux condenser, phenylhydrazine hydrochloride (8.90 mmol) was added to a solution of the Compound 1 obtained from above (8.90 mmol) in glacial acetic acid (14.3 mL). The solution obtained was stirred at 120° C. for 12 hours and thin layer chromatography (TLC) was utilized to monitor the reaction. After the reaction completed, the resulting reaction mixture was cooled to room temperature, and DI water (14.3 mL) was added. The obtained light yellow powders were filtered and washed with water and petroleum ether to give Compound 2 with a yield of 88%. ¹H NMR (400 MHz, CDCl₃, ppm): δ 8.28 (s, 1H), 7.63-7.65 (d, J=8.0 Hz, 1H), 7.48-7.50 (m, J=8.0 Hz, 2H), 7.41-7.45 (m, 3H), 7.30-7.37 (m, 5H), 7.24-7.28 (m, J=14.8 Hz, 1H), 7.15-7.19 (m, 1H).

LC-MS-ESI (m/z): calculated mass for C₂₀H₁₄BrN: 347.03. found (M+H)⁺: 348.

Synthesis of Compound 3

In a 100 mL three-neck flask equipped with a reflux condenser, the Compound 2 obtained above (3.48 g, 10 mmol, 348 g/mol), iodobenzene (6.12 g, 30 mmol, 204 g/mol), K₃PO₄ (6.36 g, 30 mmol, 212 g/mol), N,N′-dimethylethylenediamine (88 mg, 1.0 mmol, 88 g/mol) and CuI (190 mg, 1.0 mmol, 190.5 g/mol) were added and followed by adding toluene (40 mL). The mixture was stirred at reflux under N₂ atmosphere for 12 hours. After the reaction completed, the reaction mixture was extracted with ethyl acetate (EtOAc) (60 mL) and washed with brine (2×150 mL). The resulting organic phase was washed by a saturated solution of NaHCO₃ (150 mL) and dried over anhydrous Na₂SO₄, and solvent in the organic phase was removed by distillation under reduced pressure to give crude products, which were further purified by silica gel chromatography column and recrystalized to give grey powders of Compound 3 with a yield of 85%. ¹H NMR (400 MHz, CDCl₃, ppm): δ 7.75-7.76 (d, J=6.0 Hz, 1H), 7.62-7.64 (d, J=8.0 Hz, 1H), 7.43-7.45 (d, J=8.4 Hz, 1H), 7.31-7.39 (m, 5H), 7.19-7.24 (m, 5H), 7.15-7.17 (m, 2H), 7.06-7.13 (m, 3H). LC-MS-ESI (m/z): calculated mass for C₂₆H₁₈BrN: 423.06. found (M+H)⁺: 424.0689.

Synthesis of Compound 4

The Compound 2 obtained above (1.0 mmol, 348 g/mol, 348 mg) was added into a three-neck flask in THF (20 mL), and then cooled to 0° C. NaH (1.5 mmol, 24 g/mol, 36 mg) was added into the solution at 0° C. After 30 minutes, iodomethane (MeI) (1.5 mmol, 142 g/mol, 213 mg) was added and TLC was utilized to monitor the reaction. After the reaction completed, DI water was added to quench the reaction. The reaction mixture was extracted with EtOAc and washed with brine. The resulting organic phase was dried over anhydrous Na₂SO₄, and solvent in the organic phase was removed by distillation under reduced pressure to give crude products. The crude products were purified via recrystalization in anhydrous ethyl alcohol (EtOH) to give light yellow powders of Compound 4 with a yield of 95%. ¹H NMR (400 MHz, CDCl₃, ppm): δ 7.73-7.75 (d, J=8.0 Hz, 1H), 7.37-7.43 (m, 6H), 7.30-7.34 (m, 3H), 7.18-7.22 (m, 1H), 7.15-7.17 (m, 2H), 3.67 (s, 3H). LC-MS-ESI (m/z): calculated mass for C₂₁H₁₆BrN: 361.05. found (M+H)⁺: 362.0562.

Example (Ex) 1 Synthesis of HTL-1

The Compound 3 obtained above (424 mg, 1.0 mmol, 424 g/mol), N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (542 mg, 1.5 mmol, 361.5 g/mol), NaOBu^(−t) (145 mg, 1.5 mmol, 96 g/mol), X-Phos (24 mg, 5% mmol, 476.7 g/mol) and Pd(OAc)₂ (11 mg, 5% mmol, 224.5 g/mol) were added into a 100 mL 3-neck flask in Toluene (30 mL), and the solution was stirred at 110° C. under N₂ atmosphere for 4 hours. The reaction mixture was washed with brine (2×150 mL) and a saturated solution of NaHCO₃ and then extracted with EtOAc (60 mL). The resulting organic phase was dried over anhydrous Na₂SO₄, and solvent in the organic phase was removed by distillation under reduced pressure to give crude products. The crude products were further purified in silica gel column chromatography and recrystalized to give white powders of HTL-1 with a purity of 99.7% as determined by HPLC and a yield of 91%. ¹H NMR (400 MHz, CD₂Cl₂, ppm): δ 7.81-7.83 (m, 1H), 7.60-7.67 (m, 4H), 7.52-7.54 (d, J=8.4 Hz, 2H), 7.38-7.45 (m, 5H), 7.26-7.35 (m, 9H), 7.17-7.24 (m, 10H), 7.11-7.13 (d, J=6.8 Hz, 3H), 1.43 (s, 6H). LC-MS-ESI (m/z): calculated mass for C₅₃H₄₀N₂: 704.32. found (M+H)⁺: 705.3279. The obtained HTL-1 has a HOMO level of −4.64 eV, a LUMO level of −0.89 eV, a triplet energy of 2.60 eV, and a hole mobility level of 0.25, as determined by the modeling method described above. The structure of HTL-1 obtained above is shown as follows,

Ex 2 Synthesis of HTL-2

In a 100 mL three-neck flask, the Compound 4 obtained above (362 mg, 1.0 mmol, 362 g/mol), N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (542 mg, 1.5 mmol, 361.5 g/mol), NaOBu^(−t) (145 mg, 1.5 mmol, 96 g/mol), X-Phos (24 mg, 5% mmol, 476.7 g/mol) and Pd(OAc)₂ (11 mg, 5% mmol, 224.5 g/mol) were added and followed by adding toluene (30 mL). The resulting solution was stirred at 110° C. under N₂ atmosphere for 12 hours. After the reaction completed, the reaction mixture was washed with brine and extracted with EtOAc. The resulting organic phase was dried over anhydrous Na₂SO₄, and solvent in the organic phase was removed by distillation under reduced pressure to give crude products. The crude products were purified via silica gel column chromatography, and subsequently recrystalized to give white powders of HTL-2 with a purity of 99.8% as determined by HPLC and a yield of 92%. ¹H NMR (400 MHz, CDCl₃, ppm): δ 7.81-7.83 (m, 1H), 7.60-7.67 (m, 4H), 7.52-7.54 (d, J=8.4 Hz, 2H), 7.38-7.45 (m, 5H), 7.26-7.35 (m, 7H), 7.17-7.24 (m, 8H), 7.11-7.13 (d, J=6.8 Hz, 3H), 3.69 (s, 3H), 1.43 (s, 6H). LC-MS-ESI (m/z): calculated mass for C₄₈H₃₈N₂: 642.30. found (M+H)⁺: 643.3101. The structure of HTL-2 is shown as follows.

HTL-2 obtained above has a HOMO level of −4.62 eV, a LUMO level of −0.87 eV, a triplet energy of 2.60 eV, and a hole mobility level of 0.24, as determined by the modeling method described above.

Thermal properties of HTL-1 and HTL-2 were analyzed by DSC and TGA and results are shown in Table 1. As shown in Table 1, HTL-1 has a T_(g) of 124.1° C. and a T_(d) of 401.4° C.; and HTL-2 has a T_(g) of 111.0° C. and a T_(d) of 363.7° C.

TABLE 1 Sample Name T_(d) [° C.] T_(g) [° C.] T_(m) [° C.] HTL-1 401.4 124.1 N/A* HTL-2 363.7 111.0 N/A* *No obvious melting point (T_(m)), as measured by DSC, was observed.

Exs 3-4 and Comp Ex A OLED Device Fabrication

All organic materials were purified by sublimation before deposition. OLEDs were fabricated onto an ITO (Indium Tin Oxide) coated glass substrate that served as the anode, and topped with an aluminum cathode. All organic layers were thermally deposited by chemical vapor deposition, in a vacuum chamber with a base pressure of <10⁻⁷ torr. The deposition rates of organic layers were maintained at 0.1˜0.05 nm/s. The aluminum cathode was deposited at 0.5 nm/s. The active area of the OLED device was “3 mm×3 mm,” as defined by the shadow mask for cathode deposition.

Each cell containing HIL (hole injection layer), HTL, EML (emitting material layer), ETL and EIL (electron injection layer), based on materials listed in Table 2, was placed inside a vacuum chamber, until it reached 10⁻⁶ torr. To evaporate each material, a controlled current was applied to the cell, containing the material, to raise the temperature of the cell. An adequate temperature was applied to keep the evaporation rate of the materials constant throughout the evaporation process.

For the hole injection layer, N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl]-4,4′-diamine was evaporated at a constant 1 A/s rate, until the thickness of the layer reached 600 Angstrom. Simultaneously, the compound of the hole injection layer was evaporated at a constant 1 A/s rate, until the thickness reached 200 Angstrom. N4,N4′-di(naphthalen-1-yl)-N4,N4′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (NPB) was used as a reference material to compare with the inventive compounds.

For the emitting material layer, 9,10-di(naphthalen-2-yl)anthracene (ADN, host) and (E)-9,9-dimethyl-7-(4-(naphthalen-2-yl(phenyl)amino)styryl)-N,N-diphenyl-9H-fluoren-2-amine (dopant) were co-evaporated, until the thickness reached 350 Angstrom. The deposition rate for host material was 1.0 A/s, and the deposition for the dopant material was 0.02 A/s, resulting in a 2% by weight doping of the host material.

For the electron transport layer, tris(8-hydroxyquinolinato)aluminum (Alq3) was evaporated at a constant 1 A/s rate, until the thickness reached 200 Angstrom. Finally, “20 Angstrom” of a thin electron injection layer (Liq) was evaporated at a 0.5 A/s rate.

The current-voltage-brightness (J-V-L) characterizations for the OLED devices were performed with a source measurement unit (KEITHLY 238) and a luminescence meter (MINOLTA CS-100A). Electroluminescence spectra of the OLED devices were collected by a calibrated CCD spectrograph. The results are shown in Table 3 below.

TABLE 2 Name CAS No. HIL N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H- 887402-92-8 carbazol-3-yl)-[1,1′-biphenyl]-4,4′-diamine HTL Comp Ex A: N4,N4′-di(naphthalen-1-yl)- 123847-85-8 N4,N4′-diphenyl-[1,1′-biphenyl]- 4,4′-diamine Ex 3: HTL-1 Ex 4: HTL-2 Fl Blue Host 9,10-di(naphthalen-2-yl)anthracene 122648-99-1 Fl Blue (E)-9,9-dimethyl-7-(4-(naphthalen-2- 1228810-33-0 Dopant yl(phenyl)amino)styryl)-N,N-diphenyl-9H- fluoren-2-amine ETL tris(8-hydroxyquinolinato)aluminum 2085-33-8 EIL lithium quinolate 850918-68-2

As shown in Table 3, the inventive OLED devices containing a film layer containing HTL-1 as HTL showed lower driving voltage and significantly higher luminous efficiency (31% higher), as compared to the devices comprising the comparative HTL (Comp Ex A).

As shown in Table 3, the inventive OLED devices containing a film layer containing HTL-2 as HTL showed comparable driving voltage and significantly higher luminous efficiency (28% higher) as compared to the devices comprising the comparative HTL (Comp Ex A).

TABLE 3 Luminous Voltage@ Efficiency@1000 nit 1000 nit [Cd/A (candela Device HTL [V] per ampere)] CIE* (X, Y) Comp Ex A NPB 6.7 6.1 0.148, 0.148 Ex 3 HTL-1 6.5 8.0 0.148, 0.151 Ex 4 HTL-2 6.8 7.8 0.148, 0.151 *CIE refers to International Commission on Illumination.

Ex 5 Synthesis of HTL-102

Schematic of synthesis of HTL-102 is shown as below:

To a solution of 4-Fluorophenylhydrazine hydrochloride (3.24 g, 20 mmol) in AcOH (20 mL) was added 2-(4-bromophenyl)-1-phenylethan-1-one (5.5 g, 20 mmol) at room temperature. The reaction mixture was stirred under N₂ atmosphere at 100° C. for 12 hours. TLC was used to monitor the reaction. After completion of the reaction, 100 mL DI water was added to the reaction mixture to precipitate the product. The obtained precipitate was filtered and washed with 100 mL saturated aqueous solution of NaHCO₃ and water for 3 times, then used in the next step directly. NaH (960 mg, 40 mmol) was added into this reaction mixture in 20 mL DMF. After stirring at room temperature for 30 minutes, MeI (4.26 g, 30 mmol) was added into the solution and the reaction mixture was further stirred at room temperature for 12 hours. After the completion of the reaction, 100 mL DI water was added and the precipitate was filtered out. The precipitate was further purified by column chromatography to give the pure product of Compound A. ¹H NMR (400 MHz, CDCl₃, ppm): 7.36-7.42 (m, 6H), 7.28-7.33 (m, 3H), 7.10-7.12 (m, 2H), 7.02-7.07 (m, 1H), 3.66 (s, 3H). LC-MS-ESI (m/z): calcd for C₂₁H₁₅BrFN: 379.04. found (M+H)⁺: 380.0477.

To a solution of Compound A obtained above (3.04 g, 8 mmol) and diaryl amine (3.18 g, 8.8 mmol) in PhCH₃ (50 mL) was added Pd(OAc)₂ (89.6 mg, 0.4 mmol), PCy₃HBF₄ (296 mg, 0.8 mmol) and NaOBu^(−t) (1.08 g, 11.2 mmol). The reaction mixture was stirred at 100° C. under N₂ atmosphere for 12 hours. TLC was used to monitor the reaction. After completion of the reaction, 100 mL DI water was added and the precipitate was filtered out. The precipitate was further purified by column chromatography to give the pure product of HTL-102. Repeated column and recrystallization was applied to further improve the purity to >99.5%. ¹H NMR (400 MHz, CDCl₃, ppm): 7.02-7.64 (m, 28H), 3.68 (br, 3H), 1.42 (s, 6H). LC-MS-ESI (m/z): calculated mass for C₄₈H₃₇FN₂: 660.29. found (M+H)⁺: 661.2986.

HTL-102 obtained above has a HOMO level of −4.66 eV, a LUMO level of −0.95 eV, a triplet energy of 2.61 eV, and a hole mobility level of 0.22, as determined by the modeling method described above.

Ex 6 Synthesis of HTL-93

Schematic of synthesis of HTL-93 is shown as below:

To a solution of Phenylhydrazine hydrochloride (2.88 g, 20 mmol) in AcOH (20 mL) was added 2-(4-bromophenyl)-1-(4-fluorophenyl)ethan-1-one (5.86 g, 20 mmol) at room temperature. The reaction mixture was stirred under N₂ atmosphere at 100° C. for 12 hours. TLC was used to monitor the reaction. After completion of the reaction, 100 mL DI water was added to the reaction mixture to precipitate the product. The obtained precipitate was filtered and washed with 100 mL saturated aqueous solution of NaHCO₃ and water for 3 times, then used in the next step directly. NaH (960 mg, 40 mmol) was added into this reaction mixture in 20 mL DMF. After stirring at room temperature for 30 minutes, MeI (4.26 g, 30 mmol) was added into the solution and the reaction mixture was further stirred at room temperature for 12 hours. After the completion of the reaction, 100 mL DI water was added and the precipitate was filtered out. The precipitate was further purified by column chromatography to give the pure product of Compound B. ¹H NMR (400 MHz, CDCl₃, ppm): 7.73 (d, 1H, J=8 Hz), 7.39-7.43 (m, 3H), 7.28-7.34 (m, 3H), 7.19-7.23 (m, 1H), 7.19-7.23 (m, 4H), 3.68 (s, 3H). LC-MS-ESI (m/z): calculated mass for C₂₁H₁₅BrFN: 379.04. found (M+H)⁺: 380.0437.

To a solution of Compound B obtained above (3.04 g, 8 mmol) and diaryl amine (3.18 g, 8.8 mmol) in PhCH₃ (50 mL) was added Pd(OAc)₂ (89.6 mg, 0.4 mmol), PCy₃HBF₄ (296 mg, 0.8 mmol) and NaOBu^(−t) (1.08 g, 11.2 mmol). The reaction mixture was stirred at 100° C. under N₂ atmosphere for 12 hours. TLC was used to monitor the reaction. After completion of the reaction, 100 mL DI water was added and the precipitate was filtered out. The precipitate was further purified by column chromatography to give the pure product of HTL-93. Repeated column and recrystallization was applied to further improve the purity to >99.5%. ¹H NMR (400 MHz, CDCl₃, ppm): 7.83 (br, 1H), 7.63 (d, 1H, J=5.2 Hz), 7.58 (d, 3H, J=4.8 Hz), 7.49 (d, 2H, J=5.6 Hz), 7.38-7.43 (m, 4H), 7.29-7.35 (m, 5H), 7.18-7.22 (m, 8H), 7.09-7.12 (m, 4H), 3.67 (br, 3H), 1.42 (s, 6H). LC-MS-ESI (m/z): calculated mass for C₄₈H₃₇FN₂: 660.29. found (M)⁺: 660.2933. HTL-93 obtained above has a HOMO level of −4.65 eV, a LUMO level of −0.89 eV, a triplet energy of 2.61 eV, and a hole mobility level of 0.23, as determined by the modeling method described above.

Thermal properties of HTL-102 and HTL-93 were analyzed by DSC and TGA and results are shown in Table 4. As shown in Table 4, HTL-102 has a T_(g) of 118° C. and a T_(d) of 374.6° C.; and HTL-93 has a T_(g) of 115.3° C. and a T_(d) of 382.0° C.

TABLE 4 Sample Name T_(d) [° C.] T_(g) [° C.] T_(m) [° C.] HTL-102 374.6 118 N/A* HTL-93 382.0 115.3 N/A* *No obvious melting point (T_(m)), as measured by DSC, was observed.

Exs 7-8 and Comp Ex B OLED Device Fabrication

All organic materials were purified by sublimation before deposition. OLEDs were fabricated onto an ITO coated glass substrate that served as the anode, and topped with an aluminum cathode. All organic layers were thermally deposited by chemical vapor deposition, in a vacuum chamber with a base pressure of <10⁻⁷ torr. The deposition rates of organic layers were maintained at 0.1˜0.05 nm/s. The aluminum cathode was deposited at 0.5 nm/s. The active area of the OLED device was “3 mm×3 mm,” as defined by the shadow mask for cathode deposition.

Each cell containing HIL, HTL, EML, ETL and EIL, based on materials listed in Table 5, was placed inside a vacuum chamber, until it reached 10⁻⁶ torr. To evaporate each material, a controlled current was applied to the cell, containing the material, to raise the temperature of the cell. An adequate temperature was applied to keep the evaporation rate of the materials constant throughout the evaporation process.

For the hole injection layer, N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl]-4,4′-diamine was evaporated at a constant 1 A/s rate, until the thickness of the layer reached 600 Angstrom. Simultaneously, the compound of the hole injection layer was evaporated at a constant 1 A/s rate, until the thickness reached 250 Angstrom. NPB was used as a reference material to compare with the inventive compounds.

For the emitting material layer, 9,10-di(naphthalen-2-yl)anthracene (ADN, host) and (E)-9,9-dimethyl-7-(4-(naphthalen-2-yl(phenyl)amino)styryl)-N,N-diphenyl-9H-fluoren-2-amine (dopant) were co-evaporated, until the thickness reached 200 Angstrom. The deposition rate for host material was 1.0 A/s, and the deposition for the dopant material was 0.02 A/s, resulting in a 2% by weight doping of the host material.

For the electron transport layer, 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphthalen-2-yl)-1,3,5-triazine was co-evaporated with lithium quinolate (Liq), until the thickness reached 300 Angstrom. The evaporation rate for the compound of the electron transport layer and Liq was 0.5 A/s. Finally, “20 Angstrom” of a thin electron injection layer (Liq) was evaporated at a 0.5 A/s rate.

The current-voltage-brightness (J-V-L) characterizations for the OLED devices were performed with a source measurement unit (KEITHLY 238) and a luminescence meter (MINOLTA CS-100A). Electroluminescence spectra of the OLED devices were collected by a calibrated CCD spectrograph. The results are shown in Table 5 below.

TABLE 5 Name CAS No. HIL N4,N4′-diphenyl-N4,N4′-bis(9-phenyl-9H- 887402-92-8 carbazol-3-yl)-[1,1′-biphenyl]-4,4′-diamine HTL Comp Ex B: N4,N4′-di(naphthalen-1-yl)- 123847-85-8 N4,N4′-diphenyl-[1,1′-biphenyl]- 4,4′-diamine Ex 7: HTL-102 Ex 8: HTL-93 Fl Blue Host 9,10-di(naphthalen-2-yl)anthracene 122648-99-1 Fl Blue (E)-9,9-dimethyl-7-(4-(naphthalen-2- 1228810-33-0 Dopant yl(phenyl)amino)styryl)-N,N-diphenyl- 9H-fluoren-2-amine ETL 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6- 1459162-51-6 (naphthalen-2-yl)-1,3,5-triazine EIL lithium quinolate 850918-68-2

As shown in Table 6, the inventive OLED devices (Exs 7 and 8) containing a film layer containing HTL-102 or HTL-93 as HTL, respectively, showed lower driving voltage, higher luminous efficiency and significantly higher power efficiency, as compared to the devices comprising comparative HTL (Comp Ex B).

TABLE 6 Luminous Efficiency@ Power 1000 nit Efficiency Voltage@ [Cd/A (candela @1000 nit Device HTL 1000 nit [V] per ampere)] [lm/W] Comp Ex B NPB 4.8 7.7 5.01 Ex 7 HTL-102 4.1 8.5 6.53 Ex 8 HTL-93 4.1 8.3 6.33 

What is claimed is:
 1. An organic compound having the structure represented by Formula (1):

wherein R₁, R₃, and R₄ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁₋-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; R₂ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ with R₂, R₂ with R₃, or R₃ with R₄ may optionally form one or more ring structures; R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl; R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a halogen, a cyano, a hydroxyl, a carbonyl, and a substituted amino group having the structure of

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; with the proviso that at least one of R₆ and R₇ is the substituted amino group; and L₁ and L₂ are each independently selected from the following structure:

wherein A₁ is selected from a substituted or unsubstituted heteroatom selected from O, P, S, NR′, PR′, or P(═O)R′; wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl; A₂ through A₅ are each independently selected from CR′₂ or a substituted or unsubstituted heteroatom selected from N, P, PR′₂, or P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl; A₆ through A₁₁ are each independently selected from CH, N, P, PR′₂, P(═O), or C; and provided that A₆ through A₁₁ each independently represent C only when they are bonded to the indole moiety or X; and X is a chemical bond or selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; and X may form one or more rings with the ring it is bonded to.
 2. The organic compound of claim 1, wherein L₁ and L₂ are each independently a substituted or unsubstituted C₆-C₆₀ arylene.
 3. The organic compound of claim 1, wherein the organic compound has the structure represented by Formula (2):

wherein X₁ and X₂ are each a chemical bond, or each independently selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; and X₁ and X₂ may each independently form one or more rings with the rings they are bonded to; R₁, R₃, and R₄ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; R₂ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ with R₂, R₂ with R₃, or R₃ with R₄ may optionally form one or more ring structures; R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl; and R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a halogen, a cyano, a hydroxyl, a carbonyl, and a substituted amino group having the structure of

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; with the proviso that at least one of R₆ and R₇ is the substituted amino group.
 4. The organic compound of claim 1, wherein the organic compound has the structure of Formula (3-I):

wherein A₇ and A₇′ are each C; A₆ and A₆′, A₅ through A₁₁, and A₈′ through A₁₁′ are each independently selected from CH, N, P, PR′₂, and P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl; and three or less of A₆ and A₅ through A₁₁, and three of less of A₆′ and A₈′ through A₁₁′ are N; and provided that A₆ and A₈ through A₁₁ are each independently C only when they are bonded to the indole moiety or X₁, and A₆′ and A₈′ through A₁₁′ are each independently C only when they are bonded to the indole moiety or X₂; X₁ and X₂ are each a chemical bond, or each independently selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; and X₁ and X₂ may each independently form one or more rings with the rings they are bonded to; R₁, R₃, and R₄ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; R₂ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ with R₂, R₂ with R₃, or R₃ with R₄ may optionally form one or more ring structures; R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl; and R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a halogen, a cyano, a hydroxyl, a carbonyl, and a substituted amino group having the structure of

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; with the proviso that at least one of R₆ and R₇ is the substituted amino group, and at least one of R₁ through R₄, R₆ and R₇ is F or a fluoro-containing C₁-C₃₀ alkyl or C₆-C₆₀ aryl group.
 5. The organic compound of claim 1, wherein the organic compound has the structure of Formula (3):

wherein A₇ and A₇′ are each C; A₆ and A₆′, A₈ through A₁₁, and A₈′ through A₁₁′ are each independently selected from CH, N, P, PR′₂, and P(═O); wherein each R′ is hydrogen or a C₁-C₃₀ hydrocarbyl; and three or less of A₆ and A₈ through A₁₁, and three of less of A₆′ and A₈′ through A₁₁′ are N; and provided that A₆ and A₈ through A₁₁ are each independently C only when they are bonded to the indole moiety or X₁, and A₆′ and A₈′ through A₁₁′ are each independently C only when they are bonded to the indole moiety or X₂; X₁ and X₂ are each a chemical bond, or each independently selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; and X₁ and X₂ may each independently form one or more rings with the rings they are bonded to; R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl; and R₆ and R₇ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a halogen, a cyano, a hydroxyl, a carbonyl, and a substituted amino group having the structure of

wherein Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; with the proviso that at least one of R₆ and R₇ is the substituted amino group.
 6. The organic compound of claim 1, wherein Ar₁ and Ar₂ are each independently a substituted or unsubstituted C₆-C₂₀ aryl.
 7. The organic compound of any one of claims 1-4, wherein at least one of R₁ through R₄, R₆ and R₇ is F.
 8. The organic compound of any one of claims 1-6, wherein one of R₆ and R₇ is the substituted amino group, and the other one of R₆ and R₇ is selected from hydrogen, a halogen, a substituted or unsubstituted C₆-C₆₀ aryl.
 9. The organic compound of any one of claims 1-4, wherein the organic compound is represented by Formula (2c):

wherein X₁ is a chemical bond, or selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; R₁, R₃, and R₄ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; R₂ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ with R₂, R₂ with R₃, or R₃ with R₄ may optionally form one or more ring structures; and R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl.
 10. The organic compound of any one of claims 1-4, wherein the organic compound is represented by Formula (2d):

wherein X₂ is a chemical bond, or selected from the group consisting of a substituted or unsubstituted C₁-C₅₀ alkylene, a substituted or unsubstituted C₃-C₅₀ cycloalkylene, a substituted or unsubstituted C₆-C₆₀ arylene, and a substituted or unsubstituted C₁-C₆₀ heteroarylene; Ar₁ and Ar₂ are each independently selected from the group consisting of a substituted or unsubstituted C₆-C₆₀ aryl and a substituted or unsubstituted C₁-C₆₀ heteroaryl; R₁, R₃, and R₄ are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₆-C₆₀ aryl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; R₂ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₁-C₅₀ alkoxy, a substituted or unsubstituted C₁-C₅₀ alkoxycarbonyl, a substituted or unsubstituted C₁-C₆₀ heteroaryl, a substituted or unsubstituted C₆-C₆₀ aryloxy, a substituted or unsubstituted C₆-C₆₀ arylthio, a halogen, a cyano, a hydroxyl, and a carbonyl; and R₁ with R₂, R₂ with R₃, or R₃ with R₄ may optionally form one or more ring structures; and R₅ is selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C₁-C₅₀ alkyl, a substituted or unsubstituted C₃-C₅₀ cycloalkyl, a substituted or unsubstituted C₆-C₆₀ aryl, and a substituted or unsubstituted C₁-C₆₀ heteroaryl.
 11. The organic compound of claim 1, wherein the substituted amino group is selected from the following structures (5-1) through (5-6):


12. The organic compound of claim 1, wherein L₁ and L₂ are each independently selected from the group consisting of:


13. The organic compound of any one of claims 1-6, wherein R₅ is selected from the group consisting of —CH₃, —CH₂CH₃,


14. The organic compound of any one of claims 1-4, wherein at least one of R₁ through R₄ is F and the remaining R₁ through R₄ are each hydrogen, and R₅ is —CH₃.
 15. The organic compound of claim 1, wherein the organic compound is selected from the following compounds (1) through (24):


16. The organic compound of claim 1, wherein the organic compound is selected from the following compounds (25) through (34):


17. An electronic device comprising an organic layer, wherein the organic layer comprises the organic compound of any one of claims 1-16.
 18. The electronic device of claim 17, wherein the organic layer comprises a hole transport layer, an emissive layer, an electron transport layer, or a hole injection layer.
 19. The electronic device of claim 18, wherein the electronic device is a light emitting device. 